Anthraquinones



Patented Mar. 16, 1954 AN THRAQUIN ONES Victor S. Salvin, Irvington, and Edward F.- Landau, South Orange, N. J assignors to Celanese Corporation of America, New York, N. Y., a corporation of Delaware No Drawing. Application October 25, 1951,

Serial No. 253,208

9 Claims. I

This invention relates to anthraquinones and relates more particularly to the preparation of novel anthraquinones containing a hydroxyalkylthio group in the beta position.

This application is a continuation-in-part of application S. No. 105,893, filed July 20, 1949, now abandoned.-

In the dyeing of cellulose acetate and other ,organic derivative of cellulose materials, it is common to employ dyebaths containing a mixture of dyestuifs to obtain dyeings in the desired colors and shades. One of the major problems in the preparation of such dyebaths is the dimculty in obtaining dyestuffs with similar dyeing properties. If there are employed dyebaths that contain a mixture of dyestuffs that do not have similar dyeing properties, minor variations in the composition of the dyebath may produce marked differences in the color or the shade of materials dyed therewith, which is objectionable from a commercial point of view. For example, certain dyestufis are highly sensitive to the detergents normally contained in dyebaths and, as the concentration of the detergents varies, the shade of the dyeings obtained with said dyestuffs fluctuates over a wide range. Other dyestuffs are less sensitive to the detergents contained in dyebaths and show a smaller fluctuation in shade as the concentration of the detergent varies. When dyestuffs of both types are mixed in a dyebath, any variation in the concentration of the detergent will cause a change in the color or the shade of the materials dyed therewith since the dyes will be affected in an unequal manner. As a result many dyestuffs, which are otherwise entirely suited for the dyeing of cellulose acetate and other organic derivative of cellulose materials, require the taking of special precautionary measures in order that there may be obtaineduniform dyeings from dyebaths containing the same.

It is an important objection of this invention to provide novel anthraquinone dyestuffs which will be free from the foregoing and other disadvantages of prior dyestuffs.

A further object of this invention is the provision of certain novel anthraquinones containing hydroxyalkylthio groups in the beta position, which are not sensitive to the concentration of detergent in a dyebath and which will dye cellulose acetate and other organic derivative of cellulose materials in valuable blue shades.

Another object of this invention is the provision of a novel process for introducing a hydroxyalkylthio group into the beta position of an anthraquinone nucleus.

Other objects of this invention will be apparent from the following detailed description and claims. 1

stuffs of the following general formulae:

OH o on R S-(CH2) -OH NH; 0 NIH and mac on S(OH:).,OH

l I OH 0 NH:

wherein R. is H or -S-(CH2)n-OH and n is an integer, exhibit substantially no sensitivity to the concentration of detergent in a dyebath and will dye cellulose acetate and other organic derivative of cellulose materials in valuable blue shades, which are of excellent resistance to light, washing and acid-fading. Because the novel dyestuffs of our invention are not sensitive to the concentration of detergents, dyebaths containing the same yield more uniform and more level dyeings than dyebaths containing prior commercial blue dyestufis. In addition, our novel dyestuffs have a greater intrinsic color value and may be employed in lower concentrations than said prior commercial blue dyestuffs. These properties are of particular importance when the novel dyestuffs of our invention are employed in dyebaths containing a mixture of dyestuffs, since it permits said dyebaths to be readily controlled to yield dyeings that are reproducible both as to color and shade.

The dyestuffs of our invention may be prepared by a single stage process in which an anthraquinone of the following general formulae:

OH O OH I II I R SO2OH ll NH: O NH: and

ITIHQ (H) OH SO2OH 011 I 0 NH:

wherein R1 is H or SOzOH is reacted in an alkaline mediumwithra merpapto alky-l alcohol. Suitable mercaptoFjalky-l alcohols are1ferexample$2=men capto ethanol, 3-mercapto-1-propanol and 4- mercapto-l-butanol, which will yield the ;dyestuffs 1,5-dihydroxy-2-hydroxyethylthio-4,8-diamino-anthraquinone, 1,5-dihydroxyl'6di-zhydroxyethylthio-4,8-diamino anthraquinona.l 1,5- dihydroxy 2 -hydrxprop5flthio -4g thraquinone, 1,5-dihydroi3i2 ;6-dihydr ypropyl thio-4,8-diamino-anthraquinone, 1,5-dihydicoxy- 2 hydroxybutylthio-4,8-dianiino anthraquinone, 1,5 dihydroxy 2,6 di-hydroxybiityltmog ge diamino-anthraquinone, and the corresponding"l,8- dihydroxy-4,5-diamino anthraquinones M ,The res-l action medium may be rendered alkaline by any wr ta e alkal -i ms? hv as, r; exa

"soznumf hydroxide 'oripof "smm hydroxide,

In carrying tnisreaetiomrrom aboutl to mols of the mercapto alkyli alcohol, for each sulionic acid group it is desired to replace, are mixed with one-mol of an anthraquinone-psulfonic acid and a suitable alkaline agent, and the mixture so formed maintained at an elevated temperature of from about 90 to 105 C. until the reaction is complete, say for about 3.5 to 8 hours.

The following examples are, given to illustrate this invention further.

l EaampZe I A mixture of 120 parts byweight of 1,5-dihydroxy-Z sulfonic acid-4,8 'diamino-anthraquinone of 33% strength, 46 parts by weight of 2- mercapto ethanol, SOparts by weight of a 50% c; aqueouswisodiunl lhydroxide; solution, rand-@2000 l-reaction vessel-equipped '-with =a stirrer and a efluxcondensert- The mixturetis heated to' reflux 100L105" C19 i-tvith stirring'iior 5 h'ours' follown'goiwhich it iscooled and-filtered. There are r, btained ie-warts by-iweight 'o f80% strength or :w-290-% oiilth'eoretical of th'e dyestufi- -l;5-dihydroxyr. z22i+hydroxyethylthiol 4;8 dia mino-anthraquinone.

lea-E am e H ""dybath is' prepared" by dis'per'sing 0 1 part w b eight-. (ifthedyestulfor Example I inan queous bath 'containing 750 parts 'by weight of ate'ia 0'1075; sari; by weight ofeen soapy 1.5 j parts by weight of 'I Iir-keyred oil-and 0. 3-'7 5-'part yf by weight' of potassium 'pyrophosphate.'* --G'ellulose i acetate -fabrics; when dyed inthis dyebath (ii-1 h'ourfatatemperature or 80"- 62, exhibit a ing and acid fading.

-Exaimpil e' III AI fidyeliath is preparedb nisp'ersing- Oshpart by weight of theldyestufi of Example I in an aqueous bath containingfISO parts by weight of water, 2 .515 parts by weight of green soap, 1.5 parts by weight of Turkey red oil and 0.375 part by weight of potassium pyrophosphate. Cellulose acetate fabrics, when-dyed in this dyebath for 1 hour at a temperature of 80 0., exhibit a blue shade substantially identical to that obtained when the dyebath of Example II isemployed although the concentration of green soap is increased fifty foldjlpther commercial dyestuffs when dyed un'der 'conditions identical to those set forth in Examples II and III exhibit a marked variation in shade as the concentration of green soap is varied.

While our invention has' been described more 'parts -bymveight of -IMaterl are entered into a 4 particularly in connection with the dyeing of cellulose acetatematerials; thenorganic derivative of cellulose materialstmay also be dyed with our dyestufis. Examples of such materials are cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate- -propionate and cellulose acetate-butyrate and celluloseether s such as ethyl cellulose. The dye- Sstuffs' of ou a invention may also be employed 'for the d-yeing 'of other materials such as polyg,-,carboxyamides:-and polyurethanes.

H It is to be understood that the foregoing deg tailed description is given merely by way of illustration and that many variations may be made .--;;therein without departing from the spirit of our invention. y; -Having described our. invention; .-xvhat: we desire to secure by -lietters Patent is:

- 1.- Anthraqumone dyestuffs ofuthe-ggroupoconsisting of and f ji THz wherein R is. afmember or ihfegroupcqnsistme of H and -S v(CH2)n OI-Il'andfn'is' a positive integer.

2. The anth1'aquinone".dy'e stiiif l;5-dihydroxy- 2 -hydroxyeth'ylthio -4;8- dijainino fanthraquinone. 3. Process forpreparing anthraquinones, hav- .ing a hydroxyalkylthio substituent.which...com-

prises reacting a-mercaptoalkyl alcohol with an anthraquinone of v the .group} consisting of and and

NH: O 0

group consisting with one mcl of an anthraquinone of the group consisting of on o on lbw-8030K H I NH: 0 NH: and

ITTH: 0 0H S0:|OH

I OH (H) NH:

R a e lawman NH! O H! and NH: 0 OH 011 II N111 wherein R1 is a member of the group consisting of H and SO2OH at a temperature of from about to C. for about 3.5 to 8 hours.

7. Process for preparing anthraquinones having a hydroxyalkylthio substituent which comprises reacting from about 1 to 5 mols of a mercapto alkyl alcohol for each sulfonic acid group with one mol of an anthraquinone of the group consisting of OH fl) ]OH R -SO2OH I II I NH: O NH! and 11TH: OH

' SO2OH i I OH I NH:

wherein R1 is a member of the group consisting of H and SOzOH at a temperature of from about 90 to 105 C. for about 3.5 to 8 hours in the presence of an alkaline agent.

8. Process for preparing anthraquinones having a hydroxyalkylthio substituent which comprises reacting 2-mercapto-ethanol with 1,5-dihydroxy- 2-sulfonic acid-4,8-diamino-anthraquinone.

9. Process for preparing anthraquinones having a hydroxyalkylthio substituent which comprises reacting 46 parts by weight of 2-mercapto ethanol with parts by Weight of 1,5-dihydroxy-2-su1- fonic acid-4,8-diamino anthraquinone at a temperature of 100-150" C. for about 5 hours in the presence of 50 parts by weight of a 50% aqueous sodium hydroxide solution.

VICTOR S. SALVIN. EDWARD F. LANDAU.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,117,569 Peter May 17, 1938 2,434,765 Grossmann Jan. 20, 1948 2,441,355 Grossmann May 11, 1948 2,485,197 Grossmann Oct. 18, 1949 OTHER REFERENCES Beilstein: vol. 14, 4th ed., pages 873-874, 1931. 

1. ANTHRAQUINONE DYESTUFFS OF THE GROUP CONSISTING OF 